CN111269347A - Dichloroethylene-acrylic ester copolymer emulsion and preparation method thereof - Google Patents
Dichloroethylene-acrylic ester copolymer emulsion and preparation method thereof Download PDFInfo
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- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
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- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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Abstract
The invention discloses a dichloroethylene-acrylate copolymer emulsion and a preparation method thereof, comprising the following steps: ethylene dichloride: 30 to 35 percent; class a reactive monomers: 5-10%, B-type reactive monomer: 0.5-2%, C-type reactive monomer: 0.5-1%, reaction stabilizer: 0.001-0.01%, reactive anionic emulsifier: 0.5-1%, nonionic emulsifier: 0.5-1%, accelerator: 0.00002%, deionized water: 45-55%, redox initiator: 0.05 to 0.3 percent; according to the invention, through the processes of pre-emulsion preparation, seed emulsion preparation, emulsion dropwise addition polymerization and curing, the defects of the conventional emulsifier are made up, and the water resistance, the adhesive force and the salt spray resistance of a paint film are improved; the preparation system belongs to strong acid type emulsion, can react with metal substrates such as steel plates and the like, is beneficial to emulsion breaking and substrate combination of the emulsion in the film forming process, and further improves the compactness, water resistance and chemical resistance of the film.
Description
Technical Field
The invention relates to the technical field of emulsion preparation for metal coatings, in particular to a dichloroethylene-acrylate copolymer emulsion and a preparation method thereof, which are mainly applied to the metal corrosion prevention field of locomotives, steel structures, automobile chassis and the like.
Background
The existing emulsion for the metal anticorrosive paint is usually aqueous one-component chloro-meta emulsion, and the emulsion has the defects of poor heat resistance, poor salt spray resistance, poor adhesion with metal substrates and the like;
the existing conventional aqueous single-component polyvinylidene chloride emulsion adopts a thermal initiation reaction system, the proportion of effective substances in the formula is unreasonable, for example, the proportion of the selection and the content of dichloroethylene is not scientific, the molecular weight of the obtained adhesive film is low, the barrier property of a later-period paint film is poor, and the salt spray resistance of a final product is influenced;
for example: the invention relates to a preparation method of styrene-acrylate copolymer emulsion for antirust paint, which has the following patent application numbers: 201110064224.5, the invention relates to a new method for preparing styrene-acrylate copolymer emulsion for antirust priming paint, which comprises the following steps:
(1) the phosphate functional monomer is adopted to participate in emulsion polymerization, two hydroxyls of the phosphate group and the metal surface generate chelation reaction to form a compact phosphate protective film on the metal surface, so that water molecules and other salt ions are prevented from contacting the metal, the phosphate group is introduced to improve the adhesive force between the coating and the metal surface, and the antirust capability of the coating is improved;
(2) selecting diacetone acrylamide (DAAM) and Adipic Dihydrazide (ADH) to form a crosslinking system of the antirust emulsion. The dehydration condensation reaction is carried out between hydrazine group (NH2-NH2) in adipyl hydrazine and ketone carbonyl (C ═ O) in diacetone acrylamide copolymerized to the polymer, and a latex film with a three-dimensional network structure is formed through external crosslinking;
(3) the complex of the reactive anionic emulsifier and the nonionic emulsifier is used as an emulsifying system, so that the adverse phenomena of emulsion precipitation, gelation and the like are improved, the preparation of the high-solid-content water-based emulsion is facilitated, and the performances such as water resistance, weather resistance and the like are improved.
In addition to the functional monomers described in the examples, the main improvement of the technology is to use a novel redox system, and use a reaction stabilizer, especially a formaldehyde-free reducing agent, to obtain an emulsion with good heat resistance, which is superior to the emulsion prepared by the prior art.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a dichloroethylene-acrylate copolymer emulsion and a preparation method thereof, overcomes the defects of poor heat resistance, poor salt spray resistance and the like of the prior art, adopts a novel redox reaction system, and adds a functional monomer capable of forming a chemical bond with metal to obtain a high-performance anticorrosive emulsion with high molecular weight, good film forming property, good adhesive force and excellent salt spray resistance.
In order to achieve the above objects, the present invention provides a high-performance modified vinylidene chloride-acrylate copolymer emulsion and a preparation method thereof, wherein:
a dichloroethylene-acrylate copolymer emulsion comprises the following components in percentage by mass:
1. ethylene dichloride: 30 to 35 percent;
as an illustration, the ethylene dichloride employs: 1, 1-dichloroethylene;
2. class a reactive monomers: 5 to 10 percent;
further, the A-type reaction monomer is: one or a combination of methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, isooctyl acrylate or styrene;
3. b type reaction monomer: 0.5-2%;
further, the B-type reactive monomer is: one or a combination of acrylic acid, methacrylic acid, itaconic acid or 2-acrylamido-2-methylpropanesulfonic acid;
4. class C reactive monomers: 0.5-1%;
further, the C-type reactive monomer is: one or a combination of glycidyl methacrylate, methacrylamide ethyl urea ethoxy ester or 2-hydroxyethyl methacrylate phosphate;
furthermore, the addition of the A, B, C three types of reaction monomers effectively improves the adhesive force, hardness and salt spray resistance of a paint film;
5. reaction stabilizer: 0.001-0.01%;
as an illustration, the reaction stabilizer employs: ethylene diamine tetraacetic acid salt;
6. reactive anionic emulsifier: 0.5-1%;
by way of illustration, the reactive anionic emulsifier is one or a combination of α -allyl alkylphenol polyoxyethylene ether ammonium sulfate, long-chain alkyl alcohol polyoxyethylene ether methacrylate or phosphate ester of aliphatic ethoxy ethanol;
furthermore, the reactive anionic emulsifier is added, so that the influence of the conventional emulsifier on the performance of the paint film is effectively reduced, and the water resistance of the paint film is improved;
7. non-ionic emulsifier: 0.5-1%;
as an illustration, the nonionic emulsifier is: isomeric C12-C13 alcohol polyoxyethylene ethers;
8. redox initiator: 0.05 to 0.3 percent;
further, the redox initiator includes: an oxidizing agent and a reducing agent, wherein the molar ratio of the oxidizing agent to the reducing agent is 1: 1;
as an illustration, the oxidizing agent is: ammonium persulfate, tert-butyl hydroperoxide; the reducing agent is: sodium bisulfite, ascorbic acid, FF 6M;
9. accelerator (b): 0.00002%
Further, the accelerator is: ferrous sulfate heptahydrate;
furthermore, due to the addition of the redox initiator, the formaldehyde content in the copolymerization emulsion is greatly reduced, and the problems of overproof formaldehyde content and thermal yellowing resistance of emulsion products in the prior art are solved;
10. deionized water: 45 to 55 percent;
the preparation method of the dichloroethylene-acrylate copolymer emulsion comprises the following steps:
step one, pre-emulsion preparation: stirring reactive anionic emulsifier, nonionic emulsifier, dichloroethylene, A-type reaction monomer, B-type reaction monomer, C-type reaction monomer and deionized water at room temperature for 0.5 hour at a high speed to prepare a pre-emulsion;
step two, seed emulsion preparation: stirring, dissolving and mixing deionized water and a reaction stabilizer in a reaction kettle, introducing nitrogen into the dissolved mixture to remove oxygen, heating the mixed liquid to 55 ℃, and adding the mixed liquid into the pre-emulsion prepared in the step one with the weight value of 5-10% to obtain seed emulsion; then adding 30% of oxidant solution, 30% of reducing agent solution and all the accelerators in sequence;
step three, emulsion dropwise adding polymerization: after the seed emulsion reaction system obtained in the step two turns blue, dropwise adding the residual pre-emulsion and the residual redox initiator at the same time; the dripping time of the residual pre-emulsion is controlled to be 6-8 hours, the dripping of the residual oxidant solution is completed, the dripping of the residual 70 percent reducing agent solution is simultaneously completed, and the dripping time is controlled to be 8-10 hours;
step four, curing: and (5) after the dropwise adding in the third step is finished, preserving the heat for 0.5 hour, cooling, releasing the pressure, inspecting, discharging and packaging.
As an illustration, the mass ratio of the vinylidene chloride and the acrylic ester of the present invention (30 to 35): (5-10), and adjusting the actual use mass ratio, the redox initiator dosage, the reaction temperature and the reaction time of the redox initiator and the initiator in the ranges to realize the technical scheme of the invention;
has the advantages that:
(1) the system adopts the reactive emulsifier, makes up the defects of the conventional emulsifier, and improves the water resistance of the paint film; if the phosphate reactive emulsifier is adopted, phosphate ions are introduced into the reaction groups and form chemical bonds with the metal substrate, so that the adhesive force between the paint film and the substrate is improved, and the salt spray resistance of the paint film is improved.
(2) The reaction stabilizer EDTA is added into the system, and can generate chelate with metal ions which are easy to cause polymer degradation so as to inhibit the falling of HCl, thereby improving the color stability of the chlorine partial emulsion.
(3) By utilizing redox reaction and adopting a reducing agent without formaldehyde, the environment-friendly emulsion with high molecular weight, yellowing resistance of a paint film and combination of paint film strength and toughness is obtained.
(4) By adjusting the proportion of different types of acrylate monomers, the strength and toughness of the formed film can be changed, thereby improving the comprehensive performance of the coating.
(5) By adding the C-type reaction monomer and introducing one or more of epoxy group, amide group, phosphate group and polyurea group, the adhesive force, heat resistance and salt mist resistance of a paint film are improved, and the defects of poor adhesive force between a paint film prepared by the conventional polyvinylidene chloride emulsion and a metal substrate and poor heat resistance and aging resistance are overcome.
(6) The film forming property is improved: the preparation system belongs to strong acid type emulsion, can react with metal substrates such as steel plates and the like, is favorable for emulsion breaking and substrate combination in the film forming process of the emulsion, and improves the compactness, water resistance and chemical resistance of the film.
Drawings
FIG. 1 is a schematic diagram of the schematic design of the ethylene dichloride-acrylic ester copolymer emulsion and the preparation method thereof
Detailed Description
A preferred embodiment of the present invention will now be described in detail with reference to the accompanying drawings, shown in FIG. 1, wherein:
a dichloroethylene-acrylate copolymer emulsion comprises the following components in percentage by mass:
1. ethylene dichloride: 30 to 35 percent;
as an illustration, the ethylene dichloride employs: 1, 1-dichloroethylene;
2. class a reactive monomers: 5 to 10 percent;
further, the A-type reaction monomer is: one or a combination of methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, isooctyl acrylate or styrene;
3. b type reaction monomer: 0.5-2%;
further, the B-type reactive monomer is: one or a combination of acrylic acid, methacrylic acid, itaconic acid or 2-acrylamido-2-methylpropanesulfonic acid;
4. class C reactive monomers: 0.5-1%;
further, the C-type reactive monomer is: one or a combination of glycidyl methacrylate, methacrylamide ethyl urea ethoxy ester or 2-hydroxyethyl methacrylate phosphate;
furthermore, the addition of the A, B, C three types of reaction monomers effectively improves the adhesive force, hardness and salt spray resistance of a paint film;
5. reaction stabilizer: 0.001-0.01%;
as an illustration, the reaction stabilizer employs: ethylene diamine tetraacetic acid salt;
6. reactive anionic emulsifier: 0.5-1%;
by way of illustration, the reactive anionic emulsifier is one or a combination of α -allyl alkylphenol polyoxyethylene ether ammonium sulfate, long-chain alkyl alcohol polyoxyethylene ether methacrylate or phosphate ester of aliphatic ethoxy ethanol;
furthermore, the reactive anionic emulsifier is added, so that the influence of the conventional emulsifier on the performance of the paint film is effectively reduced, and the water resistance of the paint film is improved;
7. non-ionic emulsifier: 0.5-1%;
as an illustration, the nonionic emulsifier is: isomeric C12-C13 alcohol polyoxyethylene ethers;
8. redox initiator: 0.05 to 0.3 percent;
further, the redox initiator includes: an oxidizing agent and a reducing agent, wherein the molar ratio of the oxidizing agent to the reducing agent is 1: 1;
as an illustration, the oxidizing agent is: ammonium persulfate, tert-butyl hydroperoxide; the reducing agent is: sodium bisulfite, ascorbic acid, FF 6M;
9. accelerator (b): 0.00002%
Further, the accelerator is: ferrous sulfate heptahydrate;
furthermore, due to the addition of the redox initiator, the formaldehyde content in the copolymerization emulsion is greatly reduced, and the problems of overproof formaldehyde content and thermal yellowing resistance of emulsion products in the prior art are solved;
10. deionized water: 45 to 55 percent;
the preparation method of the dichloroethylene-acrylate copolymer emulsion comprises the following steps:
step one, pre-emulsion preparation: stirring reactive anionic emulsifier, nonionic emulsifier, dichloroethylene, A-type reaction monomer, B-type reaction monomer, C-type reaction monomer and deionized water at room temperature for 0.5 hour at a high speed to prepare a pre-emulsion;
step two, seed emulsion preparation: stirring, dissolving and mixing deionized water and a reaction stabilizer in a reaction kettle, introducing nitrogen into the dissolved mixture to remove oxygen, heating the mixed liquid to 55 ℃, and adding the mixed liquid into the pre-emulsion prepared in the step one with the weight value of 5-10% to obtain seed emulsion; then adding 30% of oxidant solution, 30% of reducing agent solution and all the accelerators in sequence;
step three, emulsion dropwise adding polymerization: after the seed emulsion reaction system obtained in the step two turns blue, dropwise adding the residual pre-emulsion and the residual redox initiator at the same time; the dripping time of the residual pre-emulsion is controlled to be 6-8 hours, the dripping of the residual oxidant solution is completed, the dripping of the residual 70 percent reducing agent solution is simultaneously completed, and the dripping time is controlled to be 8-10 hours;
step four, curing: and (5) after the dropwise adding in the third step is finished, preserving the heat for 0.5 hour, cooling, releasing the pressure, inspecting, discharging and packaging.
To better illustrate the design principle of the present invention, the following is briefly introduced by way of example of 4 sets of preparation methods:
example 1:
the preparation method of the dichloroethylene-acrylate copolymer emulsion comprises the following steps:
dissolving α -allyl alkylphenol polyoxyethylene ether ammonium sulfate 0.5g and isomeric C12-C13 alcohol polyoxyethylene ether 1.0g in deionized water 45g, adding 2-acrylamide-2-methylpropanesulfonic acid 1.0g, methacrylic acid 2.0g, methyl methacrylate 7.3g, isooctyl acrylate 13.3g, 1.4 g and 1-dichloroethylene 76.4g at the temperature of less than 30 ℃, and stirring at high speed for emulsification to obtain pre-emulsion;
adding deionized water 40g and EDTA 0.005g into a reaction kettle, vacuumizing, filling nitrogen for three times, pumping 7.25g of pre-emulsion into the reaction kettle, heating to 50 ℃, adding ferrous sulfate heptahydrate 0.0003g, tert-butyl hydroperoxide 0.03g and ascorbic acid reducing agent 0.03g, reacting for 15-30 min, and raising the reaction temperature to 55 ℃;
after the seeds are taken out of the pre-emulsion, 2g of glycidyl methacrylate is added into the pre-emulsion and fully stirred;
the temperature of the reaction kettle is kept at 55 ℃, and meanwhile, the pre-emulsion, the diluted tert-butyl hydroperoxide and the diluted FF6M reducing agent solution are added dropwise. The dropping time of the pre-emulsion is 6 hours, and the dropping time of the oxidant and the reducing agent is 8 hours; after the dropwise addition, the temperature is kept for 0.5 hour, and the 1, 1-dichloroethylene-acrylate emulsion with the solid content of about 50 percent is obtained by cooling, pressure relief, inspection and packaging. The emulsion has good storage stability, high film hardness, good water resistance, chemical resistance and salt spray resistance, and can be applied to water-based paint.
As an illustrative application, the ethylene dichloride-acrylate copolymer emulsion of example 1 was used to prepare a water-based paint having a formulation shown in Table 1:
TABLE 1 waterborne coating formulation
| Serial number | Composition of | Mass percent% |
| 1 | Emulsion of example 1 | 58 |
| 2 | AMP-95 solution | 1.0 |
| 3 | Film forming aid | 2.4 |
| 4 | Pigment paste | 37.2 |
| 5 | Substrate wetting agent | 0.2 |
| 6 | Flash rust preventive | 0.8 |
| 7 | Thickening agent | 0.4 |
The preparation method comprises the following steps:
adding the emulsion into a stirring kettle, stirring at a low speed, adding the diluted AMP-95 solution into the stirring kettle, stirring for 20min, testing the pH value of the emulsion to be 5.0-6.0, then slowly adding the No. 3-7 raw materials into the stirring kettle, stirring at a medium speed for 30-60 min, filtering, discharging and packaging. The performance of the prepared water-based paint is as follows: appearance: black, pH 4-6, solid content 45%, viscosity 60 seconds (coating-4 cups);
coating a coating with the thickness of 90-120 mu m on a steel plate with the surface subjected to sanding treatment by using sand paper, drying and curing for 4 hours at 60 ℃, testing the water resistance and the salt spray resistance according to the national standard, wherein the specific test data are shown in Table 2:
TABLE 2 coating film combination property index
Referring to table 3, it can be seen that the present invention utilizes redox reaction at low temperature, adopts reaction stabilizer and formaldehyde-free reducing agent, and well solves the temperature tolerance deficiency of the prior art; overcomes the defects of poor hardness, poor adhesion and poor salt spray resistance of the existing product.
Table 3 the differences between the properties of the paint film according to the invention and the commercial products are shown in the following figures:
example 2:
the preparation method of the dichloroethylene-acrylate copolymer emulsion comprises the following steps:
0.5g of long-chain alkyl alcohol polyoxyethylene ether methacrylate and 1.0g of isomeric C12-C13 alcohol polyoxyethylene ether are dissolved in 45g of deionized water, 1.0g of 2-acrylamide-2-methylpropanesulfonic acid, 2.0g of methacrylic acid, 13.3g of methyl methacrylate, 13.7g of isooctyl acrylate and 70g of 1 and 1-dichloroethylene are added under the condition that the system temperature is lower than 30 ℃, and the mixture is stirred and emulsified at a high speed to obtain a pre-emulsion.
Adding deionized water 40g and EDTA 0.005g into a reaction kettle, vacuumizing, filling nitrogen for three times, pumping 7.25g of pre-emulsion into the reaction kettle, heating to 50 ℃, adding ferrous sulfate heptahydrate 0.0003g, tert-butyl hydroperoxide 0.03g and ascorbic acid reducing agent 0.03g, reacting for 15-30 min, and heating to 55 ℃.
After the seeds are taken out of the pre-emulsion, 3g of glycidyl methacrylate is added into the pre-emulsion and fully stirred.
The temperature of the reaction kettle is kept at 55 ℃, and meanwhile, the pre-emulsion, the diluted tert-butyl hydroperoxide and the diluted ascorbic acid reducing agent solution are dropwise added. The dropping time of the pre-emulsion is 6 hours, and the dropping time of the oxidant and the reducing agent is 8 hours; after the dropwise addition, the temperature is kept for 0.5 hour, and the 1, 1-dichloroethylene-acrylate emulsion with the solid content of about 50 percent is obtained by cooling, pressure relief, inspection and packaging. The emulsion has good storage stability, high film hardness, good water resistance, chemical resistance and salt spray resistance, and can be applied to water-based paint.
Example 3:
the preparation method of the dichloroethylene-acrylate copolymer emulsion comprises the following steps:
0.5g of α -allyl alkylphenol polyoxyethylene ether ammonium sulfate and 1.0g of isomeric C12-C13 alcohol polyoxyethylene ether are dissolved in 45g of deionized water, 1.0g of 2-acrylamide-2-methylpropanesulfonic acid, 1.0g of methacrylic acid, 7.3g of methyl methacrylate, 13.3g of isooctyl acrylate and 76.4g of 1 and 1-dichloroethylene are added under the condition that the system temperature is lower than 30 ℃, and the mixture is stirred and emulsified at high speed to obtain a pre-emulsion.
Adding deionized water 40g and EDTA 0.005g into a reaction kettle, vacuumizing, filling nitrogen for three times, pumping 7.25g of pre-emulsion into the reaction kettle, heating to 50 ℃, adding ferrous sulfate heptahydrate 0.0003g, tert-butyl hydroperoxide 0.03g and ascorbic acid reducing agent 0.03g, reacting for 15-30 min, and heating to 55 ℃.
After the seeds are taken out of the pre-emulsion, 1g of 2-hydroxyethyl methacrylate phosphate is added into the pre-emulsion and fully stirred.
The temperature of the reaction kettle is kept at 55 ℃, and meanwhile, the pre-emulsion, the diluted tert-butyl hydroperoxide and the diluted ascorbic acid reducing agent solution are dropwise added. The dropping time of the pre-emulsion is 6 hours, and the dropping time of the oxidant and the reducing agent is 8 hours; after the dropwise addition, the temperature is kept for 0.5 hour, and the 1, 1-dichloroethylene-acrylate emulsion with the solid content of about 50 percent is obtained by cooling, pressure relief, inspection and packaging. The emulsion has good storage stability, good film adhesion, good water resistance, chemical resistance and salt spray resistance, and can be applied to water-based paint.
Example 4:
the preparation method of the dichloroethylene-acrylate emulsion comprises the following steps:
0.5g of phosphate ester of aliphatic ethoxyethanol and 1.0g of isomeric C12-C13 alcohol polyoxyethylene ether are dissolved in 45g of deionized water, 1.0g of 2-acrylamide-2-methylpropanesulfonic acid, 2.0g of methacrylic acid, 7.3g of methyl methacrylate, 9.7g of isooctyl acrylate and 80g of 1 and 1-dichloroethylene are added under the condition that the system temperature is lower than 30 ℃, and the mixture is stirred and emulsified at high speed to obtain a pre-emulsion.
Adding deionized water 40g and EDTA 0.005g into a reaction kettle, vacuumizing, filling nitrogen for three times, pumping 7.25g of pre-emulsion into the reaction kettle, heating to 50 ℃, adding ferrous sulfate heptahydrate 0.0003g, tert-butyl hydroperoxide 0.03g and reducing agent 0.03gFF6M, reacting for 15-30 min, and heating to 55 ℃.
After the seeds were taken out of the pre-emulsion, 1.7g of ethyl methyl acrylamide urea ethoxy ester was added to the pre-emulsion and stirred well.
The temperature of the reaction kettle is kept at 55 ℃, and meanwhile, the pre-emulsion, the diluted tert-butyl hydroperoxide and the diluted tartaric acid reducing agent solution are dropwise added. The dropping time of the pre-emulsion is 6 hours, and the dropping time of the oxidant and the reducing agent is 8 hours; after the dropwise addition, the temperature is kept for 0.5 hour, and the 1, 1-dichloroethylene-acrylate emulsion with the solid content of about 50 percent is obtained by cooling, pressure relief, inspection and packaging. The emulsion has good storage stability, good film-forming property of a coating film, good water resistance, chemical resistance and salt spray resistance, and can be applied to water-based paint.
As an illustration, the mass ratio of the vinylidene chloride and the acrylic ester of the present invention (30 to 35): (5-10), and adjusting the actual use mass ratio, the redox initiator dosage, the reaction temperature and the reaction time of the redox initiator and the initiator in the ranges to realize the technical scheme of the invention;
according to the emulsion prepared by the invention, through test comparison, the performance is not lower than that of foreign famous products such as DSM 202, Nuo Yu 803 and the like, the market price of the foreign products is more than 30 yuan/KG, the market positioning is high, the use is single, the processing and manufacturing cost of the emulsion is lower than that of the foreign products, the effect is better, the emulsion is energy-saving and environment-friendly, and the emulsion is suitable for popularization.
The above embodiments are only preferred embodiments of the present invention, and it should be understood that the above embodiments are only for assisting understanding of the method and the core idea of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalents and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (8)
1. The dichloroethylene-acrylate copolymer emulsion is characterized by comprising the following components in percentage by mass:
ethylene dichloride: 30 to 35 percent;
class a reactive monomers: 5 to 10 percent; the A-type reaction monomer is as follows: one or a combination of methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, isooctyl acrylate or styrene;
b type reaction monomer: 0.5-2%; the B-type reaction monomer is as follows: one or a combination of acrylic acid, methacrylic acid, itaconic acid or 2-acrylamido-2-methylpropanesulfonic acid;
class C reactive monomers: 0.5-1%; the C-type reaction monomer is as follows: one or a combination of glycidyl methacrylate, methacrylamide ethyl urea ethoxy ester or 2-hydroxyethyl methacrylate phosphate;
reaction stabilizer: 0.001-0.01%; reactive anionic emulsifier: 0.5-1%; non-ionic emulsifier: 0.5-1%; accelerator (b): 0.00002%, the accelerator being: ferrous sulfate heptahydrate; deionized water: 45 to 55 percent;
redox initiator: 0.05 to 0.3 percent; the redox initiator includes: an oxidizing agent and a reducing agent, wherein the molar ratio of the oxidizing agent to the reducing agent is 1: 1.
2. the ethylene dichloride-acrylate copolymer emulsion of claim 1 wherein the ethylene dichloride is selected from the group consisting of: 1, 1-dichloroethylene.
3. The ethylene dichloride-acrylate copolymer emulsion of claim 1 wherein the reaction stabilizer is: and (3) ethylenediamine tetraacetate.
4. The ethylene dichloride-acrylic ester copolymer emulsion of claim 1, wherein the reactive anionic emulsifier is one or a combination of α -ammonium allyl alkylphenol ethoxylate, long-chain alkyl alcohol ethoxylate methacrylate or phosphate ester of aliphatic ethoxy ethanol.
5. The ethylene dichloride-acrylate copolymer emulsion of claim 1 wherein the nonionic emulsifier is: the isomeric polyoxyethylene ethers of C12-C13 alcohols.
6. The dichloroethylene-acrylate copolymer emulsion of claim 1 wherein the oxidizing agent is: ammonium persulfate, tert-butyl hydroperoxide; the reducing agent is: sodium bisulfite, ascorbic acid, FF 6M.
7. The preparation method of the dichloroethylene-acrylate copolymer emulsion is characterized by comprising the following steps:
step one, pre-emulsion preparation: stirring reactive anionic emulsifier, nonionic emulsifier, dichloroethylene, A-type reaction monomer, B-type reaction monomer, C-type reaction monomer and deionized water at room temperature for 0.5 hour at a high speed to prepare a pre-emulsion;
step two, seed emulsion preparation: stirring, dissolving and mixing deionized water and a reaction stabilizer in a reaction kettle, introducing nitrogen into the dissolved mixture to remove oxygen, heating the mixed liquid to 55 ℃, and adding the mixed liquid into the pre-emulsion prepared in the step one with the weight value of 5-10% to obtain seed emulsion; then adding 30% of oxidant solution, 30% of reducing agent solution and all the accelerators in sequence;
step three, emulsion dropwise adding polymerization: after the seed emulsion reaction system obtained in the step two turns blue, dropwise adding the residual pre-emulsion and the residual redox initiator at the same time; the dripping time of the residual pre-emulsion is controlled to be 6-8 hours, the dripping of the residual oxidant solution is completed, the dripping of the residual 70 percent reducing agent solution is simultaneously completed, and the dripping time is controlled to be 8-10 hours;
step four, curing: and (5) after the dropwise adding in the third step is finished, preserving the heat for 0.5 hour, cooling, releasing the pressure, inspecting, discharging and packaging.
8. The method for preparing a dichloroethylene-acrylic ester copolymer emulsion according to claim 7, wherein the mass ratio interval of dichloroethylene to acrylic ester in the dichloroethylene-acrylic ester copolymer emulsion is as follows: 30-35: 5-10, and the actual use mass ratio of the two, the dosage of the redox initiator, the reaction temperature and the time are adjusted in the interval, so that the technical scheme of the invention can be realized.
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| CN111944102A (en) * | 2020-08-20 | 2020-11-17 | 北京中纺化工股份有限公司 | Textile additive for improving peel strength |
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| CN105669890A (en) * | 2016-02-02 | 2016-06-15 | 惠州市惠阳区嘉泰涂料有限公司 | PVDC (polyvinylidene chloride) emulsion for anticorrosive paint for metal as well as preparation method and application of PVDC emulsion |
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